An object of the present invention is to suppress a defect in a carbon membrane for fluid separation use with a dense carbon layer formed on a porous carbon support. The present invention is a carbon membrane for fluid separation use, including a dense carbon layer formed on a porous carbon support, wherein X<Y when the ratio of the content of silicon atoms to the total content of carbon atoms and silicon atoms at the center position in the membrane thickness direction of the porous carbon support is X (atomic %), and the ratio of the content of silicon atoms to the total content of carbon atoms and silicon atoms at the position of 3 μm from the interface between the porous carbon support and the dense carbon layer to the porous carbon support side is Y (atomic %).

A cross-linked polyimide of the reaction product of a crosslinking agent and a polyimide. The cross-linking agent having at least two cross-linking moieties and the polyimide has a plurality of polyimide chains having an aryl constituent with a moiety comprised of a reactive substituent. The polyimide has crosslinks from the reaction of the reactive substituent of the aryl constituents of the polyimide chains and the cross-linking moieties of the cross-linking agent. The cross-linking may be induced by thermally treating a mixture of the polyimide and crosslinking agent above about 150° C. to a temperature where the polyimide begins to decompose under an inert atmosphere. The membrane can be used for separations involving gases such as hydrogen and light hydrocarbons.

The present invention relates to a polymeric hollow fiber membrane and a carbon molecular sieve hollow fiber membrane, both of which have excellent gas separation performance, and processes for preparing the same. Specifically, the present invention relates to a hybrid polymeric hollow fiber membrane that comprises a glassy polymer containing fluorine and a ladder-structured polysilsesquioxane, a hybrid carbon molecular sieve hollow fiber membrane prepared by pyrolysis thereof, and processes for preparing the same. The hybrid polymeric hollow fiber membrane and the hybrid carbon molecular sieve hollow fiber membrane according to the embodiments of the present invention are excellent in gas flux and selectivity and can have a large surface area per unit volume. Thus, they can be advantageously used for separating gases with a high energy efficiency on a large scale.

The present invention provides an asymmetric modified CMS hollow fiber membrane having improved gas separation performance properties and a process for preparing an asymmetric modified CMS hollow fiber membrane having improved gas separation performance properties. The process comprises treating a polymeric precursor fiber with a solution containing a modifying agent prior to pyrolysis. The concentration of the modifying agent in the solution may be selected in order to obtain an asymmetric modified CMS hollow fiber membrane having a desired combination of gas permeance and selectivity properties. The treated precursor fiber is then pyrolyzed to form an asymmetric modified CMS hollow fiber membrane having improved gas permeance.

The invention is an improved method of making a carbon molecular sieve (CMS) membrane in which a precursor polymer is pyrolyzed to form a carbon molecular sieve membrane that is then exposed to a conditioning atmosphere comprised of a target permeate gas molecule such as ethylene when the membrane is desired to separate it from a light hydrocarbon gas stream. The exposure to the ethylene desirably occurs prior to the CMS permeance and selectivity combination substantially changing (e.g., within 5 days) of cooling from the pyrolyzing temperature. The CMS membranes have shown an improved combination of selectivity and permeance as well as stability and are useful to separate gases in gas streams such methane from natural gas, oxygen from air and ethylene or propylene from light hydrocarbon streams.

A carbonized PVDC copolymer useful for the separation of an olefin from its corresponding paraffin may be made by heating a polyvinylidene chloride copolymer film or hollow fiber having a thickness of 1 micrometer to 20 micrometers to a pretreatment temperature of 100° C. to 180° C. to form a pretreated polyvinylidene chloride copolymer film and then heating the pretreated polyvinylidene chloride copolymer film to a maximum pyrolysis temperature from 350° C. to 750° C. A process for separating an olefin from its corresponding paraffin in a gas mixture is comprised of flowing the gas mixture through the aforementioned carbonized polyvinylidene chloride (PVDC) copolymer to produce a permeate first stream having an increased concentration of the olefin and a second retentate stream having an increased concentration of its corresponding paraffin.

A process for separating hydrogen from a gas mixture having hydrogen and a larger gas molecule is comprised of flowing the gas mixture through a carbonized polyvinylidene chloride (PVDC) copolymer membrane having a hydrogen permeance in combination with a hydrogen/methane selectivity, wherein the combination of hydrogen permeance and hydrogen/methane selectivity is (i) at least 30 GPU hydrogen permeance and at least 200 hydrogen/methane selectivity or (ii) at least 10 GPU hydrogen permeance and at least 700 hydrogen/methane selectivity. The carbonized PVDC copolymer may be made by heating and restraining a polyvinylidene chloride copolymer film or hollow fiber having a thickness of 1 micrometer to 250 micrometers to a pretreatment temperature of 100° C. to 180° C. to form a pretreated polyvinylidene chloride copolymer film and then heating and restraining the pretreated polyvinylidene chloride copolymer film to a maximum pyrolysis temperature from 350° C. to 750° C.

The invention is an improved method of making a carbon molecular sieve (CMS) membrane in which a polyimide precursor polymer is pyrolyzed to form a carbon molecular sieve membrane by heating, in a furnace, said polyimide precursor polymer to a final pyrolysis temperature of 600 C to 700 C at a pyrolysis heating rate of 3 to 7 C/minute from 400 C to the final pyrolysis temperature, the final pyrolysis temperature being held for a pyrolysis time of at most 60 minutes in a non-oxidizing atmosphere. In a particular embodiment, the cooling rate from the pyrolysis temperature is accelerated by methods to remove heat. The CMS membranes have shown an improved combination of selectivity and permeance as well as being particularly suitable to separate gases in gas streams such methane from natural gas, oxygen from air and ethylene or propylene from light hydrocarbon streams.

The invention is an improved method of making an improved carbon molecular sieve (CMS) membrane in which a precursor polymer (e.g., polyimide) is pyrolyzed at a pyrolysis temperature to form a CMS membrane that is cooled to ambient temperature (about 40° C. or 30° C. to about 20° C.). The CMS membrane is then reheated to a reheating temperature less than the pyrolysis temperature to form the improved CMS membrane. The improved CMS membranes have shown an improved combination of selectivity and permeance as well as stability for separating hydrogen from gas molecules (e.g., methane, ethane, propane, ethylene, propylene, butane, carbon dioxide, nitrogen, butylene, and combinations thereof).

Disclosed is a method of manufacturing a partially freestanding two-dimensional crystal film (16, 16′), the method comprising providing a substrate (10) carrying a catalyst layer (14) for forming the two-dimensional crystal layer on a first surface; forming the two-dimensional crystal film on the catalyst layer; covering at least the two-dimensional crystal film with a protective layer (18); etching a cavity (24) in a second surface of the substrate, the second surface being opposite to the first surface, said cavity terminating on the catalyst layer; etching the exposed part of the catalyst layer from the cavity; and removing the protective layer, thereby obtaining a two-dimensional crystal film that is freestanding over said cavity. A device manufactured in this manner is also disclosed.